Comprehensive Evaluation of Zeolite/marine Alga Nanocomposite in The Removal of Waste Dye From Industrial Wastewater

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OPEN Comprehensive evaluation

of zeolite/marine alga
nanocomposite in the removal
of waste dye from industrial
wastewater
Ahmed Hamd 1, Mohamed Shaban 2,3, Ghadah M. Al‑Senani 4, Mashael N. Alshabanat 4,
Azza Al‑Ghamdi 5,6, Asmaa Ragab Dryaz 7, Sayed A. Ahmed 7,8, Refat El‑Sayed 9,10 &
N. K. Soliman 1*
A systematic study integrating laboratory, analytical, and case study field trial was conducted to
figure out the effective adsorbent that could be used for the removal of Congo red (CR) dye from
industrial wastewater effluent. The ability of the zeolite (Z) to adsorb CR dye from aqueous solutions
was evaluated after it was modified by the Cystoseira compressa algae (CC) (Egyptian marine algae).
Zeolite, CC algae were combined together in order to form the new composite zeolite/algae composite
(ZCC) using wet impregnation technique and then characterized by the aid of different techniques.
A noticeable enhancement in the adsorption capacity of newly synthesized ZCC was observed if
compared to Z and CC, particularly at low CR concentrations. The batch style experiment was selected
to figure out the impact of various experimental conditions on the adsorption behavior of different
adsorbents. Moreover, isotherms and kinetics were estimated. According to the experimental results,
the newly synthesized ZCC composite might be applied optimistically as an adsorbent for eliminating
anionic dye molecules from industrial wastewater at low dye concentration. The dye adsorption on Z
and ZCC followed the Langmuir isotherm, while that of CC followed the Freundlich isotherm. The dye
adsorption kinetics on ZCC, CC, and Z were agreed with Elovich, intra-particle, and pseudo-second-
order kinetic models, correspondingly. Adsorption mechanisms were also assessed using Weber’s
intraparticle diffusion model. Finally, field tests showed that the newly synthesized sorbent has a
98.5% efficient in eliminating dyes from industrial wastewater, authorizing the foundation for a recent
eco-friendly adsorbent that facilitate industrial wastewater reuse.
No one can deny that water is a vital source of life on Earth. Although industrialization and innovation have
enhanced mankind’s way of life, they are also the main cause of pollution to clean water resources1. Heavy metal,
dye, pharmaceutical, and surfactant molecules, personal care items, pesticides, and some other substances are
not only daily sources that pollute pure and restricted water resources daily but also have a dangerous effect on
all living t hings2–6. Synthetic dyes that are used in a variety of industries, including paper, rubber, textiles, dyes,
1
Basic Science Department, Faculty of Oral and Dental Medicine, Nahda University Beni-Suef (NUB), Beni
Suef, Egypt. 2Department of Physics, Faculty of Science, Islamic University of Madinah, Madinah 42351, Saudi
Arabia. 3Nanophotonics and Applications Lab, Physics Department, Faculty of Science, Beni-Suef University,
Beni Suef 62514, Egypt. 4Department of Chemistry, College of Science, Princess Nourah Bint Abdulrahman
University, P.O. Box 84428, 11671 Riyadh, Saudi Arabia. 5Department of Chemistry, College of Science, Imam
Abdulrahman Bin Faisal University, P.O. Box 1982, 31441 Dammam, Saudi Arabia. 6Renewable and Sustainable
Energy Unit, Basic and Applied Scientific Research Center (BASRC), Imam Abdulrahman Bin Faisal University,
P.O. Box 1982, 31441 Dammam, Saudi Arabia. 7Department of Chemistry, Faculty of Science, Beni-Suef University,
Beni Suef 62511, Egypt. 8Basic Science Department, Faculty of Engineering, Nahda University Beni-Suef (NUB),
Beni Suef, Egypt. 9Department of Chemistry, University College in Al‑Jamoum, Umm Al-Qura University, Mekka
25376, Saudi Arabia. 10Chemistry Department, Faculty of Science, Benha University, Benha, Egypt. *email:
nofal.khamis@nub.edu.eg
Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 1
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printing leave, plastics, and cosmetics are the source behind a bulky number of contaminants in the w ater2,7.
This huge expansion in dye usage has led to water pollution and environmental problems. These dyes are largely
non-degradable, stable, and t oxic2,8. Dyes cause mutations, respiratory toxicity, chromosomal fractions, and
cancer9. For example, people exposed to Congo red (CR) dye, will suffer from extreme eye and skin irritation
that are relieved within minutes. Besides, consuming CR can lead to stomach irritation, nausea, vomiting, and
diarrhea10. These pollutants have been removed using a variety of physical, chemical, and biological techniques.
This was accomplished by the use of reverse osmosis, coagulation, electrochemical, membrane separation process,
dilution, flotation, filtration, and softening t echniques11–13.
Compared with the above methods, adsorption is one of the most convenient used method because of low-
cost, modest, and low-maintenance, and it is straightforward to handle, with smaller quantities of sediment
than other m ethods14–20. In past decades, clay minerals, biomass wastes, agricultural residues algae, fly ash, and
activated carbon have been used as effective and cheap adsorbents for eliminating dye from wastewater21–30.
Because there are active function groups, (for example, carboxylic, hydroxyl, amino, carbonyl, phosphates,
sulfonic), pollutants attached to the wall of the biomaterials. In addition, zeolite (Z) has traditionally been used
for water softening; It is also used in wastewater treatment, catalytic processes, alternative Z production, dis-
infection purposes, construction, pulp and paper, coatings, membrane separation, refractories, ceramics, and
plastics industries31–33.
In our work, a comprehensive study including experiments and field tests is carried out to find out the most
suitable adsorption condition that effectively removes CR dyes, from industrial wastewater. Under different
experimental conditions, the adsorption performances of Z, Cystoseira compressa algae (CC), and zeolite/
algae composite (ZCC) for CR dye removal from wastewater were examined. The influence of CC on Zeolite’s
adsorption capability has been also followed up. CC and Z were nominated for a variety of reasons, including
being abundant and low-cost, natural adsorbents. In addition, the expenses of Z, CC, and ZCC regeneration and
reuse are lower, which could help make this a viable process. Definitely, the reuse of a low-cost adsorbent helps
reduces the residue removal cost. The effects of contact times, initial dye concentrations, temperature, adsorbents
doses, and pH values on CR elimination and their adsorption kinetics and isotherms were investigated using
batch experiments.
Materials and methods

Materials. CR dye was purchased from Sigma Aldrich and dissolved in distilled water. CC algae were deliv-
ered in dry form from El-Nile company. Zeolite ore was obtained from El-Nasr Mining Company and used as
it is without further modification. Sodium hydroxide granules with a purity of 99.99% and HCl (36%) were
purchased from Sigma Aldrich for pH adjustment.
Preparation of zeolite/CC algae composite (ZCC). Wet hydrothermal impregnation technique was
used to fabricate ZCC c omposite34,35. Here equal weights of zeolite and dry CC algae were combined in small
amount of distilled H2O and magnetically stirred for 60 min at 500 rpm, followed by 60 min in an ultrasonic
bath to form a paste and to attain a homogeneous impregnation of CC in the surface of Z support. The obtained
paste was dried in a vacuum oven at 60 °C for 24 h. The Z, CC, and ZCC composite were characterized by Fourier
transformer infrared (FTIR) spectrometer, X-ray diffractometer (XRD), and Scanning electronic microscopy
(SEM).
Preparation of the adsorbate. In this work, the adsorbate was chosen to be CR, a common anionic dye.
CR is the sodium salt of 3,3′-([1,1′-biphenyl]-4,4′-diyl)bis(4-aminonaphthalene-1-sulfonic acid)with a formula:
C32H22N6Na2O6S2 as shown in Fig. S1 (Supplementary data). CR stock solution of concentration of 1000 ppm
was prepared by dissolving 1 g of CR dye in 1 L of distilled H
2O. CR solutions were prepared at various concen-
trations using the diluting method. The pH was adjusted to 3, 5, 7, and 10 by adding 0.1 M NaOH or 0.1 M HCl
solution to the solution.
Adsorption studies. Four sequences of adsorption experiments were carried out on Z, CC, and ZCC adsor-
bents under various adsorption conditions. The studied adsorption parameters are starting CR concentration,
adsorbent dose, temperature, and the solution’s pH value, Table S1 (Supplementary data). All CR adsorption
studies were carried out using batch experiments under a variety of adsorption parameters; adsorption time (up
to 480 min), CR starting concentration (5–25 mg/L), pH (3–10), temperature (25–90 °C), and adsorbent dose
(0.01–0.05 g per 20 mL of CR solution) with continuous shaking.
The CR solution volume was fixed at 20 mL in each experiment. By tracking the absorption peak, the CR
concentration variation was evaluated with a Perkin Elmer Lambda 950 UV/Vis/NIR spectrophotometer. Z, CC
and ZCC reusability were investigated for four cycles where 20 mg of each adsorbent was added to 20 mL of the
CR dye with initial concentration 10 mg/L and the experiments were conducted for 480 min at fixed conditions
of temperature and pH (25 °C and pH7). After each run; the adsorbent was removed from the solution, washed
with distilled water and prepared for the next run.
The CR removal % as well as the CR elimination amounts after a period t ( qt) and at equilibrium ( qe) were
calculated using Eqs. 1 and 236,37.
(C0 − Ci )
CR dye removal % = × 100 (1)
C0
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V
qi = (C0 − Ci ) ; i = e, t (2)
m
At which C o is the CR starting concentration in mg/L and C t is the CR concentration after time t (i = t) and
e is the CR concentration at equilibrium (i = e). V is volume in mL, and m is the mass of the adsorbents in mg.
C
The existing data points are the averages of three separate trials.
Adsorption isotherms. The adsorption isotherms of the fabricated Z, CC, and ZCC nanocomposite for the
studied CR were explained using Freundlich, Langmuir, and Temkin m odels38–40. In supplementary data more
details regarding the adsorption isotherms equations and their parameters are explained. Equation 3 can be
applied to define the Langmuir isotherm’s degree of favorability for equilibrium data utilizing the dimensionless
separation factor’s value (RL)41.
1
RL = (3)
(1 + KL Cmax )
where Cmax denotes the CR dye maximum initial concentration.
Adsorption kinetics and mechanisms. Several adsorption mechanisms and kinetic models such as
internal particle diffusion, pseudo-first and second-order models, and Elekovech kinetic models are investigated
to determine the adsorption mechanisms and kinetics associated with CR adsorption on Z, CC and Z CC4,5,42–46.
Supplementary data presented more details about adsorption kinetics equations and their parameters. The aver-
age value of all adsorption results was measured in triplicate. OriginPro 2018 statistical functions were used to
obtain regression coefficient (R2) values for various kinetic and isothermal models.
Field experiments. The newly manufactured adsorbent was evaluated as an effective eco-friendly adsor-
bent that could be used on a large scale to get rid of industrial waste dye from industrial wastewater. In this
regard, wastewater samples containing waste dyes were delivered from a garment dyeing plant in Beni-Suef,
Egypt. The wastewater samples obtained were used without further purification or dilution. The best adsorbent
system was selected based on experimental results.
Results and discussion

Adsorbents characterizations. SEM characterization. Figure 1 shows the SEM images of Z, CC, and
ZCC adsorbent. Figure 1A, the SEM image of zeolite, showing flake like structure with different particle sizes
and rough surface with porous cavities on the surface which appears clearly in the SEM figures of natural Zeolite.
Moreover, the coincidence between SEM and XRD data appears clearly in the crystallinity of zeolite samples
revealed in SEM images. SEM images of CC alga, Fig. 1B, reveals the presence of cell wall and different porous
structure. The SEM image of CC, reveals a less porous surface that affects its surface area which in turn affects its
adsorption capacity. The roughness appearance on CC surface indicates the incorporation of different functional
groups, amine, carboxylic groups, and alkyl groups within the pores of the cell wall of CC algae. Finally, modifi-
cation of the zeolite surface with CC algae, the pores on the zeolite surface are covered with the CC particles as
shown in the SEM image of the ZCC composite. These particles are self-assembled to show a rough surface from
the agglomerated particles. SEM images of ZCC nanocomposite Fig. 1C confirm the formation of new type of
structure as one can see the roughness as well as crystalline structure which indicates the incorporation of CC
algae within the structure of zeolite.
XRD characterization. Figure 2A presents the XRD charts of Z, CC, and ZCC adsorbents. In line with other
studies findings47,48, the zeolite characteristic diffraction peaks appear at 2θ of ~ 9.85°, 22.41°, 26.15°, 26.84°,
28.12°, 30.075° and 32.04°. A d-spacing values of 3.968 Å and 3.173 Å were found for the zeolite major peaks at
22.41° and 28.12°, respectively. The primary peaks in the XRD chart of CC are found at ~ 28.50°, 29.89°, 31.85°,
40.66°, 45.57°, 50.37° and 66.52°. The typical major peaks of ZCC are shown in the XRD chart at around 10.01°,
11.32°, 17.50°, 21.8°, 22.54°, 26.32°, 26.94°, 30.05°, 32.18° and 66.97°. The average crystallite sizes were calculated
using the Scherer equation and were found to be 34.4 nm, 57.7 nm and 56.7 nm for Z, CC and ZCC, in order,
which is considered a proof for the nanostructure nature of the newly synthesized composite.
FT‑IR study. Figure 2B shows the FT-IR charts of Z, CC, and ZCC adsorbent. The spectrum showed a broad-
band at 3432, 3442, and 3452 cm−1 which are related to the inner OH stretching49–51. For zeolites, the band at
1029 cm−1 corresponds to the Si–O vibrational mode, for ZCC this band shifts to 1039 cm−160. The Si–O–Al
and octahedral aluminum (Al–OH) bands appears at 603 and 919 cm−1, respectively52. The Si–O–Si bending of
zeolite shows a band at 464 cm−1, for ZCC this band is shifted to 461 cm−152. The metal oxides bands appeared in
the region from 400 to 800 cm−153.
For the CC algae, the band attributed to the the stretching vibration of amine groups (–NH) appears at
3787 cm−1, while that of the hydroxyl group (–OH) of phenolic compounds appears at 3432 cm−1. The alkyl
groups (–CH) stretching band appears at 2915 cm−1, while the –C=O vibration band looks at 1627 cm−1. The
C–H vibration mode located at 1425 cm−154,55. The bands situated around 1019 cm−1 refer to the C–O bond
or the sulfate g roup56. The N–H stretching vibration mode of amines appears around 3300–3500 cm−1. While
the O–H stretching mode of a carboxylic group located at 2915 cm−157. In line with data obtained from other
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Figure 1. SEM images of (A) Z, (B) CC, and (C) ZCC adsorbents.
characterization techniques, both band shift and band disappearance confirms the new ZCC composite forma-
tion. Bands shift and assignment are summarized in Table S2.
Factors affecting the adsorption process. Effect of initial dye concentration. The amount of CR re-
moved by adsorption is highly dependent on the starting CR concentrations. The variations in the elimination
percent and the amount of CR adsorbed using Z, CC, and ZCC adsorbents at different initial concentrations
versus time were demonstrated in Fig. 3a–f. Throughout the first stage of the adsorption process, the dye elimi-
nation percentages and the adsorption capacities are very high. Their growth slows down until equilibrium is
reached. The presence of a large number of active sites found on the surface of the adsorbent can explain the
rapid rate of removal at the beginning of the reaction.
As the time procced, the active sites are completely occupied by CR m olecules58. This results in repulsive
hase37.
interactions between CR molecules in the attractive regions of the adsorbent and those in the bulk liquid p
Consequently, the fraction of CR released decreases as the initial CR concentration increases. Over all the tested
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Figure 2. (A) XRD and (B) FTIR charts of Z, CC, and ZCC adsorbents.
5 ppm 10 ppm 15 ppm 20 ppm 25 ppm

100
90 (a) (b) (c)
80
Dye removal %
70
60
50
40
30
20
10
0
0 50 100 150 200 250 300 350 400 450 500 0 50 100 150 200 250 300 350 400 450 500 0 50 100 150 200 250 300 350 400 450 500
Time, minutes Time, minutes Time, minutes
9 16
14
8 (d) (e) 14 (f)
12
7
12
6 10
10
qt (mg/g)
5
8
4 8
3 6
6
2 4
4
1
2
0 2
-1 0 0
0 50 100 150 200 250 300 350 400 450 500 0 50 100 150 200 250 300 350 400 450 500 0 50 100 150 200 250 300 350 400 450 500
Time, minuts Time, minutes Time, minutes
Figure 3. Impact of CR starting concentration and reaction time on the removal% and the amount of CR
adsorption at 25 °C, pH 7, and 20 mg of (a,d) Z, (b,e) CC, and (c,f) ZCC.
CR concentrations, the composite, ZCC, shown the highest adsorption efficiency, where ZCC > CC > Z shows
the CR removal % in the previous order. The amount of CR adsorbed increases as the starting CR concentra-
tion rises. This could be elucidated to the concentration gradient grows as the initial CR concentration rises,
as shown in Fig. 3d–f. Hence, the driving force grows, which is the main reason for overcoming the barrier for
mass transfer between Z, CC, and ZCC adsorbents and CR a dsorbates3,59. For CR with starting concentrations
of 25, 20, 15, 10, and 5 mg/L, the highest adsorption capacities of ZCC were reported to be 14.06, 14.36, 12.58,
9.50, and 4.90 mg/g, respectively. At pH 7 and 25 °C for CR with starting concentrations of 25, 20, 15, 10, and
5 mg/L, maximal adsorption capacities were 13.60, 12.90, 10.16, 7.80, and 4.40 mg/g for CC and 3.10, 5.90, 7.25,
7.60, and 8.10 mg/g for Z. The results indicated that the addition of CC to Z is a practicable method to improve
the CR uptake routine of Z.
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Adsorbent dosage effect. At the optimal adsorbent dosage for maximum efficiency, The influence of the adsor-
bent dosage on the CR removal% was estimated with respect to adsorption cost. This is shown graphically in
Fig. 4a, where the sorbent dosage varied from 0.01 to 0.05 g. From Fig. 4a, we notice that, for all adsorbents, the
dye removal% increases by rising the sorbent dosage from 0.01 to 0.05 g; in the case of Z adsorbent, it increased
from 46.15 to 64.61%, increased from 57.14 to 83.93% for CC adsorbent and from 84.44 to 98.00% for ZCC
adsorbent. Increasing the number of hot spots by increasing the adsorbent mass could be the reason for which
this observation could be accredited3,4,37. It was observed that significant jumps in removal occurred as the
adsorbent amount of ZCC increased from 0.01 to 0.02 g and that of Z increased from 0.01 to 0.03 g. In the case
of ZCC and Z, the variation of CR % removal was slightly reduced by increasing the sorbent dose above 0.02 g
and 0.03 g, respectively. This may be due to the “shielding effect” that occurs when the amount of adsorbent
increases. Due to the increase of adsorbent amount and the reduction of spaces between them, a dense layer is
formed on the surface of the adsorbent. The active site is hidden from the CR molecule by the formation of a
dense layer. Furthermore, CR molecules compete for a limited number of accessible active sites due to the over-
lap of Z and ZCC. Aggregation or agglomeration at high doses of Z and ZCC increases the diffusion path length
of CR adsorption, thereby reducing the adsorption rate43,60–62.
Influence of pH. pH is considered one of the most essential parameters influencing the dye removal capacity of
adsorbent in wastewater. The adsorption efficacy is affected by the pH of the solution, as the pH changes affect
the ionization degree of the adsorbate molecules as well as the surface characteristics of the adsorbent63. In the
pH range between pH 3 and pH 10, the pH influence on the CR removal percentage by Z, CC and ZCC adsor-
bents was studied as shown in Fig. 4b. A removal percentages of ~ 51.02%, 38.78%, 53.06%, and 48.98% were
recorded for Z adsorbent at pH values of 3, 5, 7, and 10, in order, using 20 mL of 10 mg/L of CR solution and
adsorbent dosage of 0.02 g. At the same previously mentioned conditions, a 67.69, 69.23%, 78.57%, and 60.60%
removal percentages were observed for the CC adsorbent while ZCC adsorbent represents removal percent-
ages 75%, 77.08%, 95.55%, and 89.58% at pH values of 3, 5, 7, and 10, respectively. Figure 4b shows that when
the pH of the solution is 7, the CR adsorption capacity of Z, CC, and ZCC reached their maximum limit. This
100
(a) 100 (b)
90
90
80
Dye removal %
Dye removal%
80
70
70
60
60 50
Z Z
CC 40 CC
50
ZCC ZCC
30
0.00 0.01 0.02 0.03 0.04 0.05 0.06 2 4 6 8 10
Adsorbent dose (g) pH
100
(c) 100 (d)
90 Z
Z
CC
80 CC
ZCC 80 ZCC
70
Dye removal %
Dye removal %
60 60
50
40
40
30 20
20
0
20 30 40 50 60 70 80 90 First Second Third Fourth
Temperature, °C Number of cycles
Figure 4. Effect of (a) adsorbent dose, (b) starting pH, (c) adsorption temperature, and (D) reusability test on
the removal% of 10 mg/L CR solutions by Z, CC, and ZCC.
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may be due to the interaction between the CR and adsorbent is more prominent than the interaction between
the adsorbent with OH− ions in the solution64. At lower pH levels, the positive charge on the solution interface
growths, and the Z, CC, and ZCC surfaces appear to be positively charged. However, due to the protonation of
the CR molecules, CR in the solution tends to be neutral. This situation leads to a reduction in the adsorption
of anionic CR as presented at pH 565. With increasing pH value, the positive charge on the solution interface
reduces and CR becomes negatively charged by the interaction with O H- ions. Hence, positively charged Z, CC,
and ZCC have a reasonable interaction with negatively charged CR molecules or with O H- ions. Therefore, when
pH exceeds7, CR adsorption decreases73.
Influence of temperature. The temperature effect is refered as a considerable physicochemical factor in the
adsorption study, due to the variation caused in the adsorption capacities of the a dsorbents66. A temperature
series was applied at temperature ranges 25, 40, 50, 60, 70, 80, and 90 °C, all data are presented in Fig. 4c.
A reverse relationship was noticed between temperature and dye removal percent. This relationship could be
ascribed by the fact that adsorption force brokendown upon exposure to temperature, this force is responsible
for dye molecule adsorption on the adsorbent surface75. Moreover, damaging and weakening of the active sites
between the adsorbent’s active binding sites and the adsorbate s pecies3,76,77. Consequently, the optimal tempera-
ture for CR adsorption onto all tested adsorbents was selected to be located between 25 and 30 °C. With the
temperature, the percentage of CR removal decreases, indicating exothermic adsorption process.
Reusability test. All adsorbents under investigation (Z, CC, and ZCC) were subjected to a reusability experi-
ment which was repeated for 4 cycles using identical adsorbent doses. The data illustrated in Fig. 4d revealed
that; the removal percentage of all adsorbents under investigation varied throughout the four adsorption cycles.
A noticeable decreaseing in the removal percent for Z adsorbent was recorded 53.06%, 40.82%, 34.69%, and
28.57%, in the 1st, 2nd, 3rd and 4th cycles, within the same order. While for CC, the dye removal percent
revealed a sharp decreased from 78.57% in the 1st cycle to 30% in the 4th cycle. Finally, the ZCC nanoadsorbent,
the dye removal percent was dropped from 95.55% in the 1st cycle to 41.67% in the 4th cycle. This behavior
could be explained by the fact that CR dye molecules upon reusability agglomorise on the surfaces of Z, CC, and
ZCC adsorbents and hence hides the adsorbent surfaces and pores from the dissolved CR molecules, resulting
in a loss in adsorption capacity67.
Adsorption isotherms. All data were fitted to Langmuir, Freundlich, and Temkin models using the statis-
tical significance of correlation coefficient ( R2) for nonlinear fitting of Ce versus q
e. Table 1 presents all values
related to of Qo, KL, KF, n, KT, B, and R2, these values were computed from the nonlinear fitting of the plots in
Fig. 5. From the data revealed in Table, CR adsorption on Z and ZCC adsorbents follows the Langmuir model
with the best R2 value. Consequently, a multilayer adsorption of CR molecules occured at the active sites on the
surface of the adsorbent under investigation. At these active sites there are unequally available heterogeneous
sites, each with varied adsorption energy and interacting molecules. The values of R 2 obtained from the fitting to
Langmuir isotherms in case of Z and ZCC adsorbents were 0.9837 and 0.9737 at 25 °C, respectively. The RL value
is less than unity, which indicates that the adsorption of CR in that studied case is v aluable68.
On the other hand, the adsorption isotherm of CR onto CC followed the Freundlich model. Consequently, a
single layer adsorption process occued on the active sites of the CC adsorbent, and no reaction occurred between
the adsorbed CR molecules. The R2 value was recored to be 0.9584 for the Freundlich isotherms of CC adsorbent,
Constant
Adsorbent R2 RL KL (L/mg) Qo (mg/g)
Langmuir isotherm
ZCC 0.9737 0.0068 5.781 14.11
CC 0.9479 0.062 0.599 14.91
Z 0.9837 0.114 0.309 9.67
Constant
Adsorbent R2 Kf n
Freundlich isotherm
ZCC 0.9099 10.03 5.69
CC 0.9584 6.02 2.92
Z 0.8960 3.25 3.02
Constant
Adsorbent R2 KT (L/mole) B (J/mol)
Temkin isotherm
ZCC 0.9640 239.68 1.91
CC 0.9540 7.81 2.69
Z 0.9569 2.93 2.12
Table 1. Isotherms parameters for CR adsorption on Z, CC, and ZCC.
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Figure 5. Plots showing the adsorption isotherms of (a) Langmuir, (b) Freundlich, and (c) Temkin for the
adsorption of CR using Z, CC, and ZCC at 25 °C and pH 7.
also the R
L value is less than unity, indicating that the CR adsorption in the investigated situation has considerable
valuability68. Moreover, The values of (1/n) in the Freundlich isotherm model in the adsorption process of CR
dye on the CC adsorbent were less than unity, which indicaded that adsorption was valuble, and heterogenisity
of the surface, with fewer interactions between adsorbed ions. Meanwhile, It refers to the CR adsorption occured
by multi-molecular and multi-anchorage adsorption mechanisms, r espectively69,70.
Adsorption kinetics. In order to study the most favourable kinetic model, the process of the adsorption
of CR on the surface of Z, CC, and ZCC adsorbents was followed at varying initial dye concentrations. t vs qt
was used and plotted in Fig. 6 in order to show the nonlinear forms of the first-order, second-order, and Elovich
kinetic models. After that, each of kinetics and statistical parameters; k1, k2, qe, β, α, and R2; were obtained and
all the data were presented in Table 2. The nonlinear regression values of the studied concentration range and
examined models which presented in Table 2 indicated that adsorption of CR onto Z surface was fitted by the
first-order kinetics at higher concentrations (15, 20, and 25 ppm). Which was confirmed and supported by the
good approximation between the estimated q e and experimental q
exp. Adsorption of CR onto Z surface was fitted
by Elovich kinetics at CR concentrations of 5 and 10 ppm indicating that adsorbent surfaces are not energetically
homogeneous. While, in case of ZCC, the Elovich kinetics found to be more suitable indicating that adsorbent
surfaces are not energetically homogeneous which also confirmed by the higher R 2 values71. Finally, the adsorp-
tion of CR molecules onto the surface of CC adsorbent follows first-order kinetics at lower concentration, while
it follows Elovich kinetics at lower concentration.
Sorption mechanism. Weber’s Intra-particle diffusions was found to be more favourable in the fitting of
the experimental findings in order to better understand the mechanisms and rate-controlling processes that
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Figure 6. (a,d and g) Pseudo-first-order, (b,e and h) Pseudo-second-order, and (c, f and i) Elovich sorption
kinetics of CR at 25 °C and pH 7 using 0.020 g of Z, CC, and ZCC, respectively.
First order Second order Elovich kinetic model

Adsorbents Conc. (ppm) qe exp qe calc k1 R2 qe exp qe calc k2 R2 β (g/mg) α (mg/min) R2
5 3.1 3.06 0.0079 0.9518 3.1 3.76 0.0023 0.9741 1.06 0.052 0.9892
10 5.9 5.82 0.0107 0.9654 5.9 6.91 0.0018 0.9807 0.64 0.166 0.9867
Z 15 7.25 7.56 0.0073 0.9948 7.25 9.80 7.020E-4 0.9934 0.36 0.089 0.9885
20 7.6 7.85 0.0075 0.9988 7.6 9.90 7.724E-4 0.9865 0.38 0.109 0.9900
25 8.1 8.63 0.0068 0.9956 8.1 11.37 5.444E-4 0.9927 0.30 0.089 0.9871
5 4.47 6.50 0.0026 0.9929 4.47 10.43 1.669E-4 0.9896 0.24 0.018 0.9884
10 7.85 10.60 0.0031 0.9933 7.85 16.59 1.244E-4 0.9919 0.15 0.036 0.9904
CC 15 10.16 16.40 0.0022 0.9848 10.16 27.18 5.003E-5 0.9841 0.09 0.038 0.9835
20 12.95 17.28 3.902E-5 0.9730 12.95 90.98 3.931E-6 0.9767 0.02 0.033 0.9768
25 13.66 18.40 1.643E-5 0.9862 13.66 183.26 9.638E-7 0.9872 0.01 0.032 0.9877
5 4.93 4.82 0.0177 0.9694 4.93 5.43 0.0044 0.9893 1.02 0.416 0.9897
10 9.55 9.60 0.0083 0.9631 9.55 11.82 7.652E-4 0.9789 0.34 0.168 0.9883
ZCC 15 12.58 13.02 0.0069 0.9731 12.58 16.61 4.173E-4 0.9818 0.22 0.163 0.9873
20 14.36 14.66 0.0060 0.9440 14.36 18.71 3.249E-4 0.9616 0.03 0.164 0.9773
25 14.06 16.81 0.0037 0.9781 14.06 24.04 1.230E-4 0.9822 0.13 0.083 0.9862
Table 2. Kinetic model parameters for CR dye adsorption on Z, CC, and ZCC. Significant values are in
[italics].
Vol.:(0123456789)
impact directly on adsorption kinetics. The nonlinear fitting of q t versus Ce, Fig. S2 (Supplementary data), sup-
ports the applicability of the intra-particle diffusion model’s. Meanwhile, each of slopes and intercepts of the
plots are utilized to compute K3 and I value, Table 3. The values of I ≠ 0 indicated that the intra-particle model
may not be the only rate-controlling process in identifying the adsorption process’ kinetics72. Moreover, the
boundary layer effect is clearly reflected by the intercept obtained in Fig. S2. The relation is a reverse on as bigger
the intercept, corresponding to more surface adsorption contributes to the rate control s tep72.
Batch experiments and comparison with other adsorbents. Depending on the experimental find-
ings obtained during laboratory tests, well-selected optimized parameters for the newly-synthesized ZCC adsor-
bent were applied in a real field experiment in order to find out the applicability of our new adsorbent in the real
industrial process. The parameters including 0.02 g of the adsorbent, room temperature, a non-changed pH of
the wastewater containing waste dye, and the contact time was adjusted at 420 min. The industrial wastewater
was subjected to scanning of wavelengths which revealed the presence of different wavelengths corresponding
to different dyes. After the experiments were reached to a completion, absorbance was recorded using the same
scanning device to estimate the removal percent of the dyes from the industrial wastewater. The promising data
revealed that the ZCC nanoadsorbent succeded to catch up the different dyes from industrial wastewater with
a 98.5% efficiency, which confirmed the foundation of new environmentally benign adsorbents that could be
applied to reuse the industrial wastewater.
Table 4 compares the adsorption capacity, q m, and dye removal percent of different studied adsorbents
reported in the past work with those of Z, CC, and ZCC for CR dye adsorption. It appears that qm values vary
broadly for different a dsorbents73–77. The results stated that Z, CC, and ZCC displayed reasonable capacities for
CR dye adsorption from aqueous solution relative to other adsorbent m aterials73–77.
Hypothesis for organic adsorption of dye over different studied adsorbents. Figures 7, 8 and 9
reveal interactions between zeolite, Cystoseira compressa, and ZCC composite surface and CR dye molecules.
These interactions summarized in hydrogen bonds between oxygen and amine group in CR dye molecule as
well as electrostatic interaction between negative and positive charges. This hypothesis confirmed by IR results.
Conclusions
A hydrothermal technique was selected for the preparation of of novel alga/zeolite composite ZCC from Z
and CC. In order to remove CR dye from industrial wastewater, ZCC was introduced as a novel adsorbent at
various conditions. The experimental results revealed that the lower the initial CR concentration, the greater
the removal percent of CR to be improved also the removal rate was high during the adsorption experiment’s
early stages. The removal% increased with increasing Z, CC, and ZCC dosage from 0.01 to 0.05 g and it highly
affected by temperature. For all adsorbents, the CR removal% increased with changing the initial pH from 3
to 10 and the supreme adsorption occurs at pH 7. The reducibility test for Z, CC, and ZCC adsorbents showed
that all the adsorbents were not favored for reuse for the CR removal. The isotherms of CR adsorption onto
Z, CC, and ZCC show that Z and ZCC adsorbents track the Langmuir isotherm models while CC follows the
Freundlich isotherm models. Moreover, the CR adsorption onto Z was well-fitted to the second-order kinetics,
while CC follows the intra-particle kinetics models. Furthermore, the CR adsorption onto the surface of ZCC
was well fitted with Elovich kinetics models. More optimistic, the field experiments showed promising results
as the ZCC nanoadsorbent succeeded to catch up the different dyes from industrial wastewater with a 98.5%
efficiency, which confirmed the new born of novel environmentally benign adsorbents that could be applied to
Intraparticle diffusion kinetic model

Adsorbents Conc. (ppm) I k3 (mg/g min1/2) R2
5 0.197 0.141 0.9889
10 0.693 0.268 0.9508
Z 15 0.130 0.360 0.9703
20 0.337 0.366 0.9808
25 0.006 0.412 0.9697
5 − 0.564 0.236 0.9658
10 − 0.940 0.414 0.9708
CC 15 − 1.418 0.533 0.9570
20 − 2.050 0.640 0.9286
25 − 2.472 0.693 0.9264
5 1.051 0.210 0.8739
10 0.656 0.445 0.9792
ZCC 15 0.438 0.601 0.9851
20 0.411 0.652 0.9929
25 − 0.622 0.673 0.9896
Table 3. Intra-particle diffusion parameters at various CR concentrations.
Vol:.(1234567890)
Adsorbent Conditions Adsorption capacity (mg/g) Removal % References

Time: 60 min
Surfactant Modified Zeolite A Synthesized from Concentration: 5-25 mg/L
73
Fly Ash pH: 7 23.99 83.89%
SMZA Temperature: 25 °C
Adsorbent dose: 10 mg
Time: 600 min
Concentration: 80 mg/L
74
Porphyrayezoensis Ueda (red alga) pH: 8 71.46 –
Temperature: 25 °C
Adsorbent dose: 5 g
Time: 1440 min
Concentration: 10 g/L
27.32 (linear form)
CTAB modified pumice (SMP) pH: 8 98.45% 75
18.81 (non-linear form)
Temperature: 25 °C
Adsorbent dosage: 140 g/L
Time: 360 min
Concentration: 10 g/L
3.87 (linear form)
Natural pumice (NP) pH: 8 98.11%
4.42 (non-linear form)
Temperature: 25 °C
Adsorbent dosage: 140 g/l
Time: 130 min
Alternanthera bettzichiana Plant powder
pH: 5 14.67 80.5% 76
(ABPP)
Temperature: 25 °C
Adsorbent dose: 2 g/L
Time: 40 min
77
Soil pH: 6.8–6.9 8.65 94%
Temperature: 30 °C
Adsorbent dosage: 2.5 g
Z Time: 420 min 8.1 65.00%
CC pH: 7 13.67 89.47% This work
Temperature: 25 °C
ZCC Adsorbent dose: 20 mg 14.06 98.50%
Table 4. Comparison of the optimized conditions, removal%, and adsorption capacity at different CR
adsorbents relative to our Z, CC, and ZCC nanoadsorbents.
reuse the industrial wastewater. Finally, the supposed mechanisms for the adsorption of CR dye over adsorbents
under investigation were in line with the data obtained from the IR charts and all the interactions summarized
in hydrogen bonds between oxygen and amine group in CR dye molecule as well as electrostatic interaction
between negative and positive charges.
Vol.:(0123456789)
NaO3S CR NH2
N N N N
Na
H NH S
H O
O
HO O O
OH
HO
HO OH
mannitol
HOH
NaO3S NH2
N N N N
HN S
H O
H O
O O O
OH
HO
HO OH
Figure 7. Adsorption mechanism of congo red dye on CC.
Vol:.(1234567890)
OH O
O H
Si Al NH SO3N
a
HO O O O
Si Si Si N
M N
O O O + N N
Al Si
O NaO3S HN
O O
O H
Zeolite Al CR
HOH
NaO3S SO3Na
N N N N
HN HN
H H
HO O O O OH
O Al O Si O Al O Si O Al O
O O O O O
Figure 8. Adsorption mechanism of congo red dye on Z.
Vol.:(0123456789)
NaO3S NH2
N N N N
CR
Na
H NH
+ H
O
S
H O O
O O
OH
O Mannitol
H + HO O
H H
O O O OH O
O O O O O Zeolite
HOH
NaO3S NH2
N N N N
HN O S
H H O
O O O
OH
O
H O O
H H
O HO OH OH OH
O O O O O
Figure 9. Adsorption mechanism of congo red dye on ZCC Composite.
Data availability
The datasets used and/or analysed during the current study available from the corresponding author on reason-
able request.
Received: 30 January 2023; Accepted: 24 April 2023
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Acknowledgements
The authors would like to extend their sincere appreciation to Princess Nourah bint Abdulrahman University
Researchers Supporting Project number (PNURSP2023R67), Princess Nourah bint Abdulrahman University,
Riyadh, Saudi Arabia.
Author contributions
Conceptualization, N.K, A.H. and M.S.; methodology, A.H., A.R.D., N.K. and M.S.; validation, A.H., N.K, A.R.D.
and M.S.; formal analysis, A.H., A.R.D., M.N, A.S.D., N.K., S.A.A. and M.S.; investigation, A.H. and M.S.;
resources, A.H., A.R.D., A.A., R. E. and M.S.; data curation, A.H., A.R.D., N.K., A.A., S.A. and M.S.; writing—
original draft preparation, A.H., A.R.D., N.K., R.E, and M.S.; writing—review and editing, A.H., N.K., and M.S.;
visualization, A.H. and M.S.; project administration, H.A., GM. and M.S.; funding acquisition, M.N., A.H. and
M.S. All authors have read and agreed to the published version of the manuscript.
Funding
This research was funded by the Princess Nourah bint Abdulrahman University Researchers Supporting Project
number (PNURSP2023R67), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary Information The online version contains supplementary material available at https://doi.org/
10.1038/s41598-023-34094-y.
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Comprehensive Evaluation of Zeolite/marine Alga Nanocomposite in The Removal of Waste Dye From Industrial Wastewater

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Comprehensive Evaluation of Zeolite/marine Alga Nanocomposite in The Removal of Waste Dye From Industrial Wastewater

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OPEN Comprehensive evaluation

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 1

Materials and methods

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 2

Results and discussion

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5 ppm 10 ppm 15 ppm 20 ppm 25 ppm

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Temperature, °C Number of cycles

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Table 1. Isotherms parameters for CR adsorption on Z, CC, and ZCC.

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 7

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 8

First order Second order Elovich kinetic model

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Intraparticle diffusion kinetic model

Table 3. Intra-particle diffusion parameters at various CR concentrations.

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 10

Adsorbent Conditions Adsorption capacity (mg/g) Removal % References

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Figure 7. Adsorption mechanism of congo red dye on CC.

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 12

Figure 8. Adsorption mechanism of congo red dye on Z.

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 13

Figure 9. Adsorption mechanism of congo red dye on ZCC Composite.

Received: 30 January 2023; Accepted: 24 April 2023

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 14

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 15

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 16

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© The Author(s) 2023

Scientific Reports | (2023) 13:8082 | https://doi.org/10.1038/s41598-023-34094-y 17

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